Herbicidal method employing chloro-methane sulfonanilides

ABSTRACT

Halogenmethylsulfonamides, preferably halogenmethylsulfonanilides which are substituted or unsubstituted in the phenyl nucleus may be used as plant influencing agents, for example as selective herbicides.

United States Patent [191 Lukaszczyk et al. [451 May 22, 1973 [54]HERBICIDAL METHOD EMPLOYING [56] References Cited CHLORO'METHANE UNITEDSTATES PATENTS SULFONANILIDES 3,246,976 4/1966 Brokke et al. ..7l/l03[75] Inventors: Alfons Lukaszczyk, Basel, Switzer- 3,046,104 1962 Ehlerset 03 l d; Georg Pi i m Loerrach 3,586,717 6/1971 Harrington ..7l/l03Germany 2,412,510 12/1946 Jones ..71/117 [73] .Assignee: Ciba Limited,Basel, Switzerland FOREIGN PATENTS OR APPLICATIONS [22] Fil d; A 22,1970 971,219 2/1962 Great Britain ..7l/l03 [21] Appl' 30,982 PrimaryExaminerLewis Gotts Assistant Examiner-Catherine L. Mills [30] ForeignAppficafim Priority Data Attorney-Harry Goldsmith, Joseph G. Kolodny andMario A. Monaco Apr. 30, 1969 Switzerland ..66l7/69 52 U S Ci [57]ABSTRACT {51% In-t -Cl 2 51333112 Halogenmethylsulfonamides, preferablyhalogen- [58] Fie'ld 71/103 methylsulfonanilides which are substitutedor unsubstituted in the phenyl nucleus may be used as plant infiuencingagents, for example as selective herbicides.

1 Claim, No Drawings 1 HERBICIDAL METHOD EMPLOYING CHLORO-METHANESULFONANILIDES This invention relates to a process for combatingundesired plant growth in crop cultures, which comprises applyinghalogenmethylsufonamides as selective herbicides or to a process ofinfluencing plants broadly. The active substances are encompassed by theformula in which X represents halogen and R stands for a phenyl radicalwhich may be unsubstituted or substituted by C,-C -alkyl,C,C.,-alkylsulfonyl, -CN, -SCN, N NO, carboxy, carbalkoxy, optionallyacetalized CHO, sulfonic acid, sulfamyl, C -c -haloaliphat, especiallyCCl,,, CCl F, CClF CF C F,, or halogen.

An especially active group of compounds of the for- The activesubstances of the formula (I) according to this invention may be presentin the formulations in ad mula (1) comprises those in which X representshalogen, especially Cl or Br, and R stands for a phenyl radical which isunsubstituted or substituted by C -C alkyl, C -C -alkyl-sulfonyl, N0 CFCCl CF Cl, CCI F or halogen.

Especially good herbicidal activity is observed when the phenyl nucleusR contains electronegative electron drawing) substituents which does notpreclude the presence of electro-neutral substituents.

In a rather narrow sense, those compounds are important in which the 2-,2,5-, 3,4-, 3,5 or 2,4,5-positions of the phenyl nucleus are occupied byidentical or different substituents of the kind mentioned. X is halogen,preferably chlorine or bromine.

For the 2-position, halogen, N0 CF CC];, or CN are preferredsubstituents.

For the 2,5-positions, halogen, N0 CCl CF CN are preferred.

For the 3,4-positions, halogen, CCl CF CN, alkoxycarbonyl,alkylsulfonyl, N0 and NO are preferred.

For the 3,5-positions, halogen, CCl CE, and N0 are preferred.

For the 2,4,5-positions, halogen, CCl CF NO, N0 CN, alkoxycarbonyl,alkylsulfonyl, CH0 and alkyl are preferred.

Halogen here denotes F, Cl, Br and 1; Cl and Br are preferred.

Unexpectedly, the herbicidal and plant-influencing action of thesulfonanilides of the formula (I) is very good. These substances aresuitable as selective herbicides in the culture of useful plants forcombating undesired broad-leafed and grass-like weeds and in additionthey favorably influence the development of crop plants. Such influenceincludes growth regulation, increasing the resistance to externalinfluences (frost, drought, salt content of the soil) and also theregulation of blossoming and ripening. Defoliating and desiccatingproperties are also observed.

The invention also comprises the use of selective herbicidal agentscontaining as active ingredient one or more than one compounds of theformula (I), together with a suitable carrier, solvent, diluent,emulsifier, dispersant, wetting agent, adhesive agent, fertilizer, orother pest combating agents or other plant influencing agents, includinggrowth hormones, such as 2,4D, 2,4DP, MCPA, MCPB, MCPP, CCC, CMH, BMH,etc.

mixture with other known active substances. The formulations as arulecontain between 0.1 and percent by weight of active substance. Theseconcentrations may vary within wide limits and in each case depend onthe most appropriate kind of formulation as solution,

emulsion, suspension, dusting powder, paste or granulate. The activesubstances of the formula (I) are formulated according to known methods.Common types of formulations are described, for example, in U.S. Pat.Nos. 3,134,665 and 3,329,702 and British Patent Specification No.1,047,644. Some typical examples are given below.

Some of the formulations may be applied over large areas by means ofaircraft (dusting, spraying).

The herbicidal agents are used in quantities of 0.01 kg/ha to 20 kg/ha,preferably between 0.1 kg/ha and 10 kg/ha.

Known weed killers may be added in order to widen the range ofusefulness. Such weed killers include:

A. Substituted Ureas N-Phenyl-N,N'-dimethyl-ureaN-(4-chlorophenyl)-N,N'-dimethyl-urea N-( 3 ,4-dichlorophenyl )-N' ,N-dimethyl-urea N-(4-chlorophenyl)-N-methoxy-N'-methyl-ureaN-(3,4-dichlorophenyl)-N-methoxy-N'-methyl-ureaN-(4-bromophenyl)-N'-methoxy-N'-methyl-ureaN(4-bromo-3-chlorophenyl)-N-methoxy-N-methylureaN(4-chlorophenyl)-N'-methyl-Nbutyl-ureaN(4-chlorophenyl)-N'-methyl-N'-isobutyl-ureaN(4chlorophenoxyphenyl)-N,N-dimethyl-urea B. Substituted triazines2-chloro-4,6-bis(ethylamino)-s-triazine2-chloro-4-ethylamino-6-isopropylamino-s-triazine2-chloro-4,6-bis(methoxypropylamino)-s-triazine2-methoxy-4,6-bis(isopropylamino)-s-triazine2-diethylamino-4-isopropylacetamido-6-methoxy-striazine2-isopropylamino-4-methoxyethylamino-6-methylmercapto-s-triazine2-methylmercapto-4,6-bis(isopropylamino)-s-triazine2-methylmercapto-4,6-bis(ethylamino)-s-triazine2-methylmercapto-4-ethylamino-6-isopropylamino-striazine2-methoxy-4,6-bis(ethylamino)-s-triazine2-methoxy-4-ethylarnino-6-isopropylamino-s-triazine2-chlor-4,6-bis(isopropylamino)-s-triazine2-methylmercapto-4-azido-6-isopropylamino-s-triazine These triazines maybe admixed with the compounds of the formula (I) in the ratios 1:10 to20:1 parts by weight.

C. Phenols Dinitro-sec-butylphenyl or salts thereof pentachlorophenol orsalts thereof D. Carbonic acids 2,3,6-trichlorobenzoic acid and salts2,3,5,-tetrachlorobenzoic acid and salts2-methoxy-3,5,6-trichlorobenzoic acid and salts2-methoxy-3,-dichlorobenzoic acid and salts 3-amino-2,S-dichlorobenzoicacid and salts 3-nitro-2,5-dichlorobenzoic acid and salts2-methyl-3,6-dichlorobenzoic acid and salts 2,4-dichlorophenoxy aceticacid and salts and esters. 2,4,5-trichlorophenoxy acetic acid and saltsand esters (2-methyl-4-chlorophenoxy) acetic acid and salts and esters2-(2,4,5-trichlorophenoxy )propionic acid and salts and esters2-(2,4,5-trichlorophenoxy )ethyl-2,2-

dichloropropionate 4-(2,4-dichlorophenoxy)butyric acid and salts andesters 4-(2-methyl-4-chlorophenoxy)butyric acid and salts and esters2,2-dichloropropionic acid E. Carbamic acid derivatives lsopropylcarbanilate m-chloro-isopropyl carbanilatem-chloro-(4-chloro-2-butinyl)-carbanilate rn-trifluoromethyl-isopropylcarbanilate F. Various compounds 2,3,6-trichlorophenyl acetic acidchloroacetic acid-diallylamide maleic acid hydrazide disodiummethylarsonic acid borates 3-amino-triazole pyrazinderivatives aspyramine endooxohexahydrophathalic acid diphenylacetonitrile TreflanBalan Planavin dimethyl-tetrachloro-phthalic acid4-trifluoromethyl-2,4'-dinitro-diphenylether2,4-dichloro-4'-nitro-diphenylether 3-cyclohexyl-6-methyluracil3-cyclohexyl-6-sec-butyluracil 3-cyclohexyl-5-bromouracil3-cyclohexyl-5-chlorouracil 3-isopropyl-5-chlorouracil3-isopropyl-5-bromouracil and other known uracils.

The sulfonanilides of the formula (I) are obtained by reacting anaromatic amine R-NH which is unsubstituted or substituted as indicated,with a halogenmethylsulfonic acid halide, for example by reacting anamine of the formula subst. 7

with halomethylsulfochloride, preferably in the presence of an acidacceptor, such as pyridine or quinoline. In the formula (ll) subst."means to of the substituents mentioned for R phenyl in formula (I).

The following Example is typical of the method of preparation.

EXAMPLE 1 In a 2.5 liter sulfonating flask, 360 g of 2,4,5-trichloraniline are stirred with 1,200 ml of pyridine. At an internaltemperature of 0 C, 276 g of chloromethanesulfochloride are addeddropwise and the mixture is stirred for 20 hours, the internaltemperature rising to room temperature. The contents of the flask arethen introduced into 2.5 liters of water and the whole aciditied with37% HCl. The aqueous phase is decanted and the oily residue is washedwith 30% NaOH. The precipchloromethansulfo.-2,5 -dichloroanilide, m .p.O7l08 C 7. chloromethansulfo-2 ,4-dichloroanilide, m.p.

8. chloromethansulfo-3,4-dichloroanilide, m.p. 88-89 C 9.chloromethansulfo-3-bromo-4-chloroanilide,

10. chloromethansulfo-3-chloro-4bromoanilide,

1 l. chloromethansulfo-3-chloro-4-jodoanilide,

l2. chloromethansulfo-3-jodo-4-chloroanilide,

l 3. chloromethansulfo-3,4-dibromoanilide,

l4. chloromethansulfo-Z-chloroanilide, m.p. 72 C 1 5.chloromethansulfo-Z-bromoanilide,

16. chloromethansulfo-2-nitroanilide,

l7. chloromethansulfo-2-trifluoromethylanilide 1 8.chloromethansulfo-2-cyanoanilide l9. chloromethansulfo-2,3,4,6-tetrachlor0anilide,

20. chloromethansulfo-pentachloroanilide,

21 chloromethansulfo-trichlorotolylaminde,

22. chloromethansulfotrichlorobutoxanilide,

23. chloromethansulfo(trichloroacetic trichloroanilide 24.chloromethansulfo(chloroacetic)-trichloroanilide, 25.chloromethansulfo-2-chloro-5- trifluoromethylanilide, m.p. 7678 C 26.chloromethansulfo-3-trifluoromethylanilide m.p. 107l08 C 27.chloromethansulfo-3,5-bis(trifluoromethyl)- anilide, m.p. 98-99 C 28.chloromethansulfo-3-cyano-5 -trifluorom ethylanilide,

29. chloromethansulfo-2-trifluoromethyl-4- chloroanilide,

30. chloromethansulfo-3-trifluoromethyl-4- chloroanilide,

3 l. chloromethansulfo-Z-fluoro-5 trifluoromethylanilide,

32. chloromethansulfo-3-nitro-5 trifluoromethylanilide,

3 3. chloromethansulfo-S -chloro-2- trifluoromethylanilide,

34. chloromethansulfo-2 ,4-dichloro-5- trifluoromethylanilide,

3 5. chloromethansulfo-2,3 ,4-trichloro-5- trifluoromethylanilide, 36.chloromethansulfo-4-(methylsulfonyl)-anilide,

37. chloromethansulfo-3-trifluoromethyl-4-methylanilide, 3 8.chloromethansulfo-3-trifluorom ethyl-4- chloroanilide, m.p. -9l C 39.chloromethansulfo-3-trifluoromethyl-4- bromoanilide,

40. chlormethansulfo-3-trifluoromethyl-4-j0doanilide, 41chloromethansulfo-2-chloro-4-nitroanilide, m.p. l l4-l 16 C 42.chloromethansulfo-3-chloro-4- trifluoromethylanilide, 43.chloromethansulfo-3-nitro-4-chloroanilide, m.p.

6 7 8. chloromethansulfo-3-bromo-5- trichloromethylanilide, I 79.chloromethansulfo-3 nitro-5- trichloromethylanilide 44.chloromethansulfo-3,S-dichloroanilide, m.p. 134 5 r h n -2.4-dichloro-5-C trichloromethylanilide, 45. chloromethansulfo-2-chloro-5-bromoanilide,ChIOI'OmethaHSUIfO-Z,5-dihl01'0-4- 46.chloromethansulfo-2-chloro-5-cyanoanilide, tfichlofomethylanilide, 47.chloromethansulfo-Z-bromo-S-chloroanilide, bIOmOmCthaHSUIfO-Z,4,5-tl'i=hl0l'0anilide, 48. chloromethansulfo-2,5-dibromoanilide, lbrom0methansulfo-pentachlomanilide,

49. chloromethansulfo-2-bromo-5-nitroanilide,bfomomethansulfOJ,4-dichlol'oanilide, 50. chloromethansulfo-2-bromo-5-85. bromomethansulfo-3-chloro-4-bromoanilide, trifluoromethylanilide,86. bromomethansulfo-3-bromo-4-chloroanilide, 51.chloromethansulfo2-bromo-5-cyanoanilide, 87.bromomethansulfo-4-chloroanilide, 52. chloromethansulfo-Z-nitro-5- I588. bromoethansulfo-4-bromoanildie, trifluoromethylanilide, 89.bromomethansulfo-3-trifluoromethylanilide 5 3.chloromethansulfo-2-nitro-5-chloroanilide, 54.chloromethansulfo-2-trifluoromethyl-5- EXAMPLES OF FORMULATIONSchloroanilide Dusting Agents igoanilidechommethansulfo'z'mfluommethyl's' Equal parts of an active substanceaccording to this invention and precipitated silica are finely ground.56. chloromethansulfo-Z-cyano-S-chloroanilide, D

. ustlng agents with a preferred content of active sub- 57.chloromethansulfo-Z-cyano-S-bromoanilide, f 58.chloromethansulfo-3,S-dichloroanilide, i"."' 1 T 6 Pace can be made by59. chloromethansulfo-3-chlorog ggsgg talcum" Strifluoromethylanilide, py g 60. chloromethansulfo-3-nitro-5-chloroanilide To obtam aSpraymgPowder for example the follow- 61 chloromethansulfo 3initm 5 mgcomponents are mixed and finely ground: tritiuoromethylanilide 50 partsof active substance according to this invention, 62.chloromethansulfo-2,4-dichloro-5-carbethoxyani- 20 parts of hlghlyadsorptw? Shca lide 25 parts of bolus alba (kaolin) 63.chloromethansulfo-Z,5-dichloro-4-nitrosoanilide, of sodmm1'benZyl'2'stearyl'benzlmldazole 64.chloromethansulfo-Z,5-dichloro-4-nitroanilide, g 65.chloromethansulfo-Z,5-dichloro-4-cyanoanilide, Concentratechloromethansulfmz,5 dichlow 4 methylcarbonyb Readily soluble activesubstances can also be formu anmde lated as emulsion concentratesaccording to the follow- 67. chloromethansulfo-Z,4-dichloro-5- mg itrifluoromethylanilidc, 20 Parts of act've Substance 68.chloromethansulfo-2,4-dibromo-5- 70 Parts of xyle netrifluoromethylanilide, 40 10 parts of a mixture of a reaction productof an alkyl 69. chloromethansulfo-2,4-dibromo-5-carbethoxyani- Phenolethylene oxide and calcium dodecylben' dc, zenesulfonate are mixed. Ondilution with water to the 70.chloromethansulfo-2,5-dibromo-4-nitrosoanilide, defsired concentration,a sprayable emulsion is 7 l.chloromethansulfo-Z,5-dibromo-4-nitroanilide, tamed- 72.chloromethansulfo-2,5-dibromo-4-methylcarbonyl- Granulates anmde, 7.5 gof one of the active substances of the formula (I) 7 3 h] th lf 2h1oro-4 5-bi rb th are dissolved in 100 ml of acetone and the resultingacilid etonic solution is poured on to 92 g of granulated atta- 74. chlr th lf g it -5 pulgite (mesh size, 24/28 meshes per inch). The wholetrichloromethylanilide, is well mixed and the solvent expelled in arotary evap- 7 5, h1 methanS If -Z- hIQm-S- orator. A granulate with a7.5 percent content of active trichloromethylanilide, substance isobtained. 76. chloromethansulfo-Z-bromo-S- trichloromethylanilide,EXAMPLE 2 77. chloromethansulfo-3-chloro-5- ln pre-emergence andpost-emergence tests, comtrichloromethylanilide, pounds of the formula(I) are very harmful to dicotylei mmg g ie 'v Z QQQQQ QAQ Avena Sotaria.Sinapis Lepidium Avena Setaria Sinapis Lepidium Compound N0.AEABABABABABABAB 1111999044449099 11 1121 2111110909 1 1 1 1 1 1 1 1 4 24 3 9 9 9 9 111121111,111'9s07 111121612222999-9 212131745475999911111142434499!!!) 111166882222989-0 1111215311440099 l1ll11311112879011l1964211321l999 1111111111119999 NOTE.A=5 kg. of active substance/ha;B=2.5 kg. of active substance/ha.

dons sown in clay pots and treated with aqueous preparations of theactive substances, whereas monocotyledons are hardly affected, if at allEXAMPLE 3 TABLE Culture Quantity used 2.0 L kg AS/ha Triticum 3 3Hordeum 4 2 Zea 2 1 Weeds Galium 6 6 Calendula 9 9 Chrysanthemum 9 9Brassica 9 9 lpomoea 9 9 Stellaria 9 9 Amaranthus 9 9 Legend: 1 3 nonoteworthy damage to the plant 4 7 damage to the plant 8 9 plant nolonger viable We claim:

1. A process for combatting weeds in the presence of crop plants whichcomprises applying to the crop growing area a herbicidally effectiveamount of chloromethanesulfone-2,4,5-trichloroanilide.

Paten N 3.7341710 Dated Muriel/973 Inventor) 4 ALFONS LUKA-S-ZCZYK andGE'ORG PISSIOTAS It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Correct the assigriee's. name to read CIBA-w'GE-IGY AG Signed end sealedthis 5th day of Fehruary 1974.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. RENE D. TEGTMEYER Attesting Officer ActingCommissioner of Patents- FORM PO-1050 (10-69) I uscoMM-oc 60876-P69 fi'LLS. GOVERNMENT PRINTING OFFICE I969 0-366-334,

